JPH04249533A - Three-dimensional network structure of aromatic polyamideamic acid and production thereof - Google Patents
Three-dimensional network structure of aromatic polyamideamic acid and production thereofInfo
- Publication number
- JPH04249533A JPH04249533A JP41886790A JP41886790A JPH04249533A JP H04249533 A JPH04249533 A JP H04249533A JP 41886790 A JP41886790 A JP 41886790A JP 41886790 A JP41886790 A JP 41886790A JP H04249533 A JPH04249533 A JP H04249533A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- aromatic polyamide
- amic acid
- network structure
- dimensional network
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 113
- 125000003118 aryl group Chemical group 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 28
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 28
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 239000004760 aramid Substances 0.000 claims description 91
- 229920003235 aromatic polyamide Polymers 0.000 claims description 91
- 239000003960 organic solvent Substances 0.000 claims description 44
- 150000001412 amines Chemical class 0.000 claims description 29
- -1 aromatic tricarboxylic acid Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 claims description 18
- 150000004984 aromatic diamines Chemical class 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 238000007363 ring formation reaction Methods 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 31
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 abstract description 2
- 150000003863 ammonium salts Chemical group 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 229920000768 polyamine Polymers 0.000 abstract 1
- 238000005316 response function Methods 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 65
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000008961 swelling Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- BXIYIGBKSGVJOS-UHFFFAOYSA-N 4-(3,4-diaminophenyl)benzene-1,2-diamine;dihydrate;tetrahydrochloride Chemical compound O.O.Cl.Cl.Cl.Cl.C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 BXIYIGBKSGVJOS-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- IGUXFXNMXMXLCK-UHFFFAOYSA-N (3-aminophenyl)-(3,4-diaminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C(N)=CC=2)=C1 IGUXFXNMXMXLCK-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- KJDSORYAHBAGPP-UHFFFAOYSA-N 4-(3,4-diaminophenyl)benzene-1,2-diamine;hydron;tetrachloride Chemical compound Cl.Cl.Cl.Cl.C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 KJDSORYAHBAGPP-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CVIUJSXIENVAGJ-UHFFFAOYSA-N 1-methyl-2H-pyrrol-2-ide Chemical compound CN1C=CC=[C-]1 CVIUJSXIENVAGJ-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- JBCUKQQIWSWEOK-UHFFFAOYSA-N 2-(benzenesulfonyl)aniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 JBCUKQQIWSWEOK-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- FJYCAYKHNVQCJW-UHFFFAOYSA-N 2-[4-[4-(2-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)C=C1 FJYCAYKHNVQCJW-UHFFFAOYSA-N 0.000 description 1
- DZLUPKIRNOCKJB-UHFFFAOYSA-N 2-methoxy-n,n-dimethylacetamide Chemical compound COCC(=O)N(C)C DZLUPKIRNOCKJB-UHFFFAOYSA-N 0.000 description 1
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- JKETWUADWJKEKN-UHFFFAOYSA-N 4-(3,4-diaminophenyl)sulfonylbenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)C1=CC=C(N)C(N)=C1 JKETWUADWJKEKN-UHFFFAOYSA-N 0.000 description 1
- HOSGAMZDLWSREP-UHFFFAOYSA-N 4-(3-aminophenyl)benzene-1,2-diamine Chemical group NC1=CC=CC(C=2C=C(N)C(N)=CC=2)=C1 HOSGAMZDLWSREP-UHFFFAOYSA-N 0.000 description 1
- ILPWTQGYOZFLBN-UHFFFAOYSA-N 4-[(3,4-diaminophenyl)methyl]benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1CC1=CC=C(N)C(N)=C1 ILPWTQGYOZFLBN-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 description 1
- 229960004012 amifampridine Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- NLNRQJQXCQVDQJ-UHFFFAOYSA-N bis(3,4-diaminophenyl)methanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=C(N)C(N)=C1 NLNRQJQXCQVDQJ-UHFFFAOYSA-N 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229940075930 picrate Drugs 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、三次元網目構造よりな
り、有機溶媒中で高分子ゲルを形成する新規な芳香族ポ
リアミドアミド酸の三次元網目構造体、及び、このもの
を脱水・閉環反応して得られた耐熱性・機械的性質に優
れた芳香族ポリアミドイミドの三次元網目構造体、並び
に、前記それぞれの三次元網目構造体の製造方法に関す
るものである。[Industrial Application Field] The present invention relates to a novel three-dimensional network structure of aromatic polyamide amic acid that forms a polymer gel in an organic solvent, and a method for dehydrating and ring-closing this structure. The present invention relates to a three-dimensional network structure of aromatic polyamideimide having excellent heat resistance and mechanical properties obtained by reaction, and a method for producing each of the three-dimensional network structures.
【０００２】0002
【従来技術及び問題点】芳香族ポリアミドイミドは、耐
熱性、機械的性質共に優れた高分子材料であり、広く工
業材料として使用されてきた。芳香族ポリアミドイミド
の重合は、芳香族トリカルボン酸とジアミンとの重縮合
反応によって、固相又は溶液中で調製されるのが一般的
である。特に、トリカルボン酸無水物のアシルハライド
誘導体と芳香族ジアミンをモノマーとして、有機溶媒中
で溶液重合させ、芳香族ポリアミドアミド酸を前駆体と
して脱水・閉環反応により芳香族ポリアミドイミドを得
る方法が、その調製法の容易さから広く用いられており
、特開昭４７−８０９３号公報、特公昭６３−５１１８
３号公報、特開昭６３−２２５６３０号公報等に示され
る通りである。しかしながら、芳香族ポリアミドイミド
及びその前駆体である芳香族ポリアミドアミド酸に関し
、多価アミンのような特定のモノマー成分を一成分とし
て使用し、有機溶媒中で重合反応させ、溶液中でポリマ
ーの分子鎖が三次元的に結合し、自重により形状が崩れ
ないような自己支持性のあるゲルを与えるような有機溶
媒を含む芳香族ポリアミドアミド酸の高分子ゲル、及び
、それを前駆体として調製された芳香族ポリアミドイミ
ドの成形体に関する報告は、殆んどなされていなかった
。[Prior Art and Problems] Aromatic polyamide-imide is a polymeric material with excellent heat resistance and mechanical properties, and has been widely used as an industrial material. Polymerization of aromatic polyamide-imide is generally prepared in a solid phase or in a solution by a polycondensation reaction between an aromatic tricarboxylic acid and a diamine. In particular, there is a method in which an acyl halide derivative of tricarboxylic acid anhydride and an aromatic diamine are used as monomers, solution polymerized in an organic solvent, and aromatic polyamideimide is obtained by dehydration and ring closure reaction using aromatic polyamideamic acid as a precursor. It is widely used due to its easy preparation method, and is disclosed in Japanese Patent Application Laid-open No. 47-8093 and Japanese Patent Publication No. 63-5118.
This is as shown in Publication No. 3, Japanese Unexamined Patent Publication No. 63-225630, and the like. However, regarding aromatic polyamide-imide and its precursor aromatic polyamide-amic acid, a specific monomer component such as a polyvalent amine is used as one component, and a polymerization reaction is performed in an organic solvent to form polymer molecules in a solution. A polymer gel of aromatic polyamide amic acid containing an organic solvent that provides a self-supporting gel in which the chains are bonded three-dimensionally and does not lose its shape under its own weight, and a polymer gel prepared using it as a precursor. There have been almost no reports regarding molded articles of aromatic polyamideimide.
【０００３】0003
【発明の目的】本発明の目的は、芳香族トリカルボン酸
無水物のアシルハライド誘導体、芳香族ジアミン及び多
価アミンを主成分としたモノマー類を有機溶媒中で反応
させることにより、新規な芳香族ポリアミドアミド酸の
高分子ゲルを形成させ、物質分離作用、刺激−応答作用
等のある多機能の芳香族ポリアミドアミド酸の三次元網
目構造体（高分子ゲル）、及び、これを前駆体として耐
熱性及び機械的性質に優れた芳香族ポリアミドイミドの
三次元網目構造体（成形体）を提供すること、並びに、
前記それぞれの三次元構造体の製造方法を提供すること
にある。OBJECT OF THE INVENTION The object of the present invention is to create a new aromatic compound by reacting monomers containing acyl halide derivatives of aromatic tricarboxylic anhydrides, aromatic diamines, and polyvalent amines in an organic solvent. A three-dimensional network structure (polymer gel) of multifunctional aromatic polyamide amic acid that forms a polymer gel of polyamide amic acid and has substance separation and stimulus-response effects, and a heat-resistant polymer gel using this as a precursor. To provide a three-dimensional network structure (molded body) of aromatic polyamideimide having excellent properties and mechanical properties, and
An object of the present invention is to provide a method for manufacturing each of the three-dimensional structures described above.
【０００４】0004
【発明の構成及び作用】本発明は、下記の通りである。Structure and operation of the invention The present invention is as follows.
【請求項１】 下記［Ａ］［Ｂ］［Ｃ］成分
を有機溶媒中で重合反応させて得た芳香族ポリアミドア
ミド酸の三次元網目構造体。
［Ａ］下式で表わされる芳香族トリカルボン酸無水物の
アシルハライド誘導体の単独又は二種以上の組み合わせ
1. A three-dimensional network structure of aromatic polyamide amic acid obtained by polymerizing the following components [A], [B], and [C] in an organic solvent. [A] Acyl halide derivatives of aromatic tricarboxylic acid anhydrides represented by the following formula alone or in combination of two or more
【化１】
（式中、Ａは三価の芳香族基、Ｘはハロゲン原子を表わ
す）
［Ｂ］下式で表わされる芳香族ジアミンの単独又は二種
以上の組み合わせ[Chemical formula 1] (In the formula, A represents a trivalent aromatic group and X represents a halogen atom) [B] An aromatic diamine represented by the following formula, alone or in combination of two or more
【化２】
（式中、Ｂは二価の芳香族基を表わす）［Ｃ］ひとつの
分子構造中に三個以上のアミン基及び／又はアンモニウ
ム塩基を有する多価アミンの単独又は二種以上の組み合
わせ[Chemical formula 2] (In the formula, B represents a divalent aromatic group) [C] Single or two or more types of polyvalent amines having three or more amine groups and/or ammonium bases in one molecular structure combination of
【請求項２】 ［Ａ］／［Ｂ］／［Ｃ］成分のモ
ル比が、１００／（５０〜１００）／（１〜２５）であ
る請求項１記載の芳香族ポリアミドアミド酸の三次元網
目構造体。2. The three-dimensional aromatic polyamide amic acid according to claim 1, wherein the molar ratio of the [A]/[B]/[C] components is 100/(50-100)/(1-25). mesh structure.
【請求項３】 ［Ａ］［Ｂ］［Ｃ］成分を主成分
としたモノマー類を有機溶媒中で重合反応させて得られ
た芳香族ポリアミドアミド酸溶液を０〜８０℃に保つこ
とで芳香族ポリアミドアミド酸の架橋反応を溶液中で進
め芳香族ポリアミドアミド酸の高分子ゲルとし、次いで
有機溶媒を除去することによる請求項１記載の芳香族ポ
リアミドアミド酸の三次元網目構造体の製造方法。3. An aromatic polyamide amic acid solution obtained by polymerizing monomers mainly composed of components [A], [B], and [C] in an organic solvent is maintained at a temperature of 0 to 80°C. The method for producing a three-dimensional network structure of aromatic polyamide amic acid according to claim 1, which comprises carrying out a crosslinking reaction of the group polyamide amic acid in a solution to form a polymer gel of aromatic polyamide amic acid, and then removing the organic solvent. .
【請求項４】 ［Ａ］［Ｂ］［Ｃ］成分を主成分
とした請求項１記載の芳香族ポリアミドアミド酸の三次
元網目構造体を５０〜４００℃の温度で少なくとも１０
秒以上処理し、脱水・閉環反応させることにより得られ
た芳香族ポリアミドイミドの三次元網目構造体。4. The three-dimensional network structure of the aromatic polyamide amic acid according to claim 1, which contains components [A], [B], and [C] as main components, at a temperature of 50 to 400°C for at least 10
A three-dimensional network structure of aromatic polyamide-imide obtained by dehydration and ring-closing reaction after being treated for more than a second.
【請求項５】 ［Ａ］［Ｂ］［Ｃ］成分を主成分
とした請求項１記載の芳香族ポリアミドアミド酸の三次
元網目構造体を５０〜４００℃の温度で少なくとも１０
秒以上処理し、脱水・閉環反応させることによる請求項
４記載の芳香族ポリアミドイミドの三次元網目構造体の
製造方法。
この有機溶媒を含む芳香族ポリアミドアミド酸の三次元
網目構造体（高分子ゲル）は、有機溶媒中で２〜５０倍
の体積膨潤度［（膨潤後の体積）／（膨潤前の溶媒を含
まない固形の体積）］を示すものであり、多量の有機溶
媒を含んでも流動を起こさず、形状を保持できるような
自己支持性のある高分子ゲルを与えるものである。また
、本発明の芳香族ポリアミドアミド酸の三次元網目構造
体は、有機溶媒の出入りにより可逆的に収縮・膨潤する
能力を有する三次元網目構造体である。ここでの三次元
網目構造体とは、主に［Ａ］成分と［Ｂ］成分とからな
る芳香族ポリアミドアミド酸の鎖状高分子を［Ｃ］成分
である多価アミンが架橋点として働き連結させ、ポリマ
ーの三次元網目構造を形成したものである。本発明では
、［Ａ］［Ｂ］［Ｃ］成分である芳香族トリカルボン酸
無水物のアシルハライド誘導体、芳香族ジアミン及び多
価アミンを重合反応させることにより、最初は有機溶媒
に均一に溶解した芳香族ポリアミドアミド酸溶液が得ら
れる。しかし、この芳香族ポリアミドアミド酸溶液の状
態は中間体的なものであり、重合場に残存する未反応の
官能基による架橋反応が有機溶媒中で徐々に進行するこ
とにより、芳香族ポリアミドアミド酸成分の三次元網目
構造が形成されゲル化を起こし、最終的には有機溶媒を
含んだ芳香族ポリアミドアミド酸の高分子ゲルが得られ
る。有機溶媒を含んだ芳香族ポリアミドアミド酸の高分
子ゲル及びこれを前駆体として脱水・閉環反応により得
られた芳香族ポリアミドイミドの成形体は、以下のよう
な手順に従って調製することができる。5. The three-dimensional network structure of the aromatic polyamide amic acid according to claim 1, which contains components [A], [B], and [C] as main components, is heated at a temperature of 50 to 400°C for at least 10
5. The method for producing a three-dimensional network structure of aromatic polyamide-imide according to claim 4, which comprises treating for more than a second to cause a dehydration/ring closure reaction. This three-dimensional network structure (polymer gel) of aromatic polyamide amic acid containing an organic solvent has a volume swelling degree of 2 to 50 times [(volume after swelling)/(including solvent before swelling) in an organic solvent. It provides a self-supporting polymer gel that does not flow and can maintain its shape even when it contains a large amount of organic solvent. Moreover, the three-dimensional network structure of aromatic polyamide amic acid of the present invention is a three-dimensional network structure that has the ability to reversibly contract and swell by entering and exiting an organic solvent. The three-dimensional network structure here refers to a chain polymer of aromatic polyamide amic acid mainly consisting of components [A] and [B], with polyvalent amines as component [C] acting as crosslinking points. They are connected to form a three-dimensional network structure of polymers. In the present invention, by polymerizing the acyl halide derivative of aromatic tricarboxylic acid anhydride, aromatic diamine, and polyvalent amine that are components [A], [B], and [C], the components are initially uniformly dissolved in an organic solvent. An aromatic polyamide amic acid solution is obtained. However, the state of this aromatic polyamide amic acid solution is that of an intermediate, and as the crosslinking reaction by the unreacted functional groups remaining in the polymerization site progresses gradually in an organic solvent, the aromatic polyamide amic acid A three-dimensional network structure of the components is formed, causing gelation, and finally a polymer gel of aromatic polyamide amic acid containing an organic solvent is obtained. A polymer gel of aromatic polyamide-amic acid containing an organic solvent and a molded article of aromatic polyamide-imide obtained by dehydration and ring-closing reaction using the polymer gel as a precursor can be prepared according to the following procedure.
【０００５】（１）有機溶媒中で、芳香族トリカルボン
酸無水物のアシルハライド誘導体、芳香族ジアミン及び
多価アミンを混合し、重合反応させることにより、有機
溶媒に均一に溶解した芳香族ポリアミトアミド酸溶液を
得る。
（２）芳香族ポリアミドアミド酸溶液がゲル化を起こす
前に賦形のために、特定の形状を持つ型に上記溶液を流
し込むか、又は、フィルム状にする場合は、基材上に流
延させる。
（３）上記溶液を０〜１００℃の間の温度条件で静置し
、芳香族ポリアミドアミド酸の未反応の官能基による架
橋反応を有機溶媒中で進行させることで三次元網目構造
を形成させ、有機溶媒を含んだ芳香族ポリアミドアミド
酸の高分子ゲルを得る。
（４）芳香族ポリアミドアミド酸の高分子ゲルから、含
まれる有機溶媒を除去し、フィルム等の成形体を得た後
、脱水・閉環反応を行わせ、芳香族ポリアミドイミドの
成形体を得る。
以下、調製方法の詳細を述べることにする。まず最初に
、有機溶媒中で芳香族トリカルボン酸無水物のアシルハ
ライド誘導体、芳香族ジアミン及び多価アミンを混合し
、重合反応させることにより、有機溶媒に均一に溶解し
た芳香族ポリアミドアミド酸溶液を調製する。芳香族ト
リカルボン酸無水物のアシルハライド誘導体、芳香族ジ
アミン及び多価アミンの重合反応において、この反応は
窒素ガスのような不活性雰囲気下、芳香族ジアミンと多
価アミンを有機溶媒中に溶解させた溶液中に攪拌させな
がら芳香族トリカルボン酸無水物のアシルハライド誘導
体を加えるのが一般的である。(1) An aromatic polyamide homogeneously dissolved in an organic solvent is obtained by mixing an acyl halide derivative of an aromatic tricarboxylic acid anhydride, an aromatic diamine, and a polyvalent amine and causing a polymerization reaction. Obtain an amic acid solution. (2) In order to shape the aromatic polyamide amic acid solution before gelation occurs, the solution is poured into a mold with a specific shape, or if it is to be made into a film, it is cast onto a base material. let (3) The above solution is allowed to stand at a temperature between 0 and 100°C, and a three-dimensional network structure is formed by allowing the crosslinking reaction of the unreacted functional groups of the aromatic polyamide amic acid to proceed in an organic solvent. , a polymer gel of aromatic polyamide amic acid containing an organic solvent is obtained. (4) After removing the organic solvent contained in the polymer gel of aromatic polyamide-amic acid to obtain a molded body such as a film, a dehydration/ring-closing reaction is performed to obtain a molded body of aromatic polyamide-imide. The details of the preparation method will be described below. First, an acyl halide derivative of aromatic tricarboxylic anhydride, an aromatic diamine, and a polyvalent amine are mixed in an organic solvent, and a polymerization reaction is performed to form an aromatic polyamide amic acid solution uniformly dissolved in the organic solvent. Prepare. In the polymerization reaction of acyl halide derivatives of aromatic tricarboxylic acid anhydrides, aromatic diamines, and polyvalent amines, this reaction involves dissolving the aromatic diamine and polyvalent amine in an organic solvent under an inert atmosphere such as nitrogen gas. The acyl halide derivative of aromatic tricarboxylic anhydride is generally added to the solution while stirring.
【０００６】芳香族トリカルボン酸無水物のアシルハラ
イド誘導体［Ａ］は、一般に下式で表わされる。The acyl halide derivative [A] of aromatic tricarboxylic acid anhydride is generally represented by the following formula.
【化１】
（式中、Ａは三価の芳香族基、Ｘはハロゲン原子を表わ
す）
式中、Ａで表わされる三価の芳香族には、下記に示すよ
うな構造のものが具体例として挙げられる。[Chemical formula 1] (In the formula, A represents a trivalent aromatic group, and X represents a halogen atom.) In the formula, specific examples of the trivalent aromatic group represented by A have the structures shown below. It is mentioned as.
【化３】[Chemical formula 3]
【化４】[C4]
【化５】[C5]
【化６】[C6]
【化７】
（但し、Ｐは−Ｏ−，−ＣＯ−，−ＣＨ２−，−ＳＯ２
−又は−Ｓ−を表わす）
これらは、単独又は二種以上の混合物で用いることがで
きる。芳香族トリカルボン酸無水物のアシルハライド誘
導体と反応させる芳香族ジアミン［Ｂ］の代表例として
は、メタフェニレンジアミン、パラフェニレンジアミン
、４，４′−ジアミノジフェニルプロパン、４，４′−
ジアミノジフェニルメタン、３，３′−ジアミノジフェ
ニルメタン、４，４′−ジアミノジフェニルスルフィド
、４，４′−ジアミノジフェニルスルホン、３，３′−
ジアミノジフェニルスルホン、３，４′−ジアミノジフ
ェニルスルホン、４，４′−ジアミノジフェニルエーテ
ル、３，３′−ジアミノジフェニルエーテル、３，４′
−ジアミノジフェニルエーテル、４，４′−ジアミノベ
ンゾフェノン、３，３′−ジアミノベンゾフェノン、２
，２′−ビス（４−アミノフェニル）プロパン、ベンジ
ジン、３，３′−ジアミノビフェニル、２，６−ジアミ
ノピリジン、２，５−ジアミノピリジン、３，４−ジア
ミノピリジン、ビス［４−（アミノフェノキシ）フェニ
ル］スルホン、ビス［４−（３−アミノフェノキシ）フ
ェニルスルホン、ビス［４−（４−アミノフェノキシ）
フェニル］エーテル、ビス［４−（３−アミノフェノキ
シ）ェニル］エーテル、２−２′−ビス［４−（４−ア
ミノフェノキシ）フェニル］プロパン、２，２′−ビス
［４−（３−アミノフェノキシ）フェニル］プロパン、
４，４′−ビス（４−アミノフェノキシ）ビフェニル、
１，４−ビス（４−アミノフェノキシ）ベンゼン、１，
３−ビス（４−アミノフェノキシ）ベンゼン、２，２′
−ビス［４−（３−アミノフェノキシ）フェニル］ヘキ
サフロロプロパン、１，５−ジアミノナフタレン、２，
６−ジアミノナフタレン及びこれらの誘導体等が挙げら
れる。これらは、単独又は二種以上の混合物で用いるこ
とができる。[Chemical 7] (However, P is -O-, -CO-, -CH2-, -SO2
- or -S-) These can be used alone or in a mixture of two or more. Typical examples of the aromatic diamine [B] to be reacted with the acyl halide derivative of aromatic tricarboxylic acid anhydride include meta-phenylene diamine, para-phenylene diamine, 4,4'-diaminodiphenylpropane, 4,4'-
Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'
-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 2
, 2'-bis(4-aminophenyl)propane, benzidine, 3,3'-diaminobiphenyl, 2,6-diaminopyridine, 2,5-diaminopyridine, 3,4-diaminopyridine, bis[4-(amino phenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenylsulfone, bis[4-(4-aminophenoxy)
phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 2-2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(3-amino) phenoxy) phenyl] propane,
4,4'-bis(4-aminophenoxy)biphenyl,
1,4-bis(4-aminophenoxy)benzene, 1,
3-bis(4-aminophenoxy)benzene, 2,2'
-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 1,5-diaminonaphthalene, 2,
Examples include 6-diaminonaphthalene and derivatives thereof. These can be used alone or in a mixture of two or more.
【０００８】多価アミン［Ｃ］とは、ひとつの分子構造
中に三個以上のアミン基及び／又はアンモニウム塩基を
有する化合物を示す。多価アミンの代表としては、３，
３′，４，４′，−テトラアミノジフェニルエーテル、
３，３′，４，４′−テトラアミノジフェニルメタン、
３，３′，４，４′−テトラアミノベンゾフェノン、３
，３′，４，４′−テトラアミノジフェニルスルホン、
３，３′，４，４′−テトラアミノビフェニル、１，２
，４，５−テトラアミノベンゼン、３，３′，４−トリ
アミノジフェニルエーテル、３，３′，４−トリアミノ
ジフェニルメタン、３，３′，４−トリアミノベンゾフ
ェノン、３，３′，４−トリアミノジフェニルスルホン
、３，３′，４−トリアミノビフェニル、１，２，４−
トリアミノベンゼン及びこれらの化合物の官能基を第四
アンモニウム塩の形に変えた化合物類、例えば３，３′
，４，４′−テトラアミノビフェニル・四塩酸塩等が挙
げられる。第四アンモニウム塩としては塩酸塩の他に、
Ｐ−トルエンスルホン酸塩、ピクリン酸塩等の形で用い
ることもできる。これらの化合物の中には、多価アミン
の官能基の全てが第四アンモニウム塩の形でないものも
含まれる。また、上記物質の中には水和物として存在し
ているものもあり、これらの多価アミン類は単独又二種
以上の混合物で用いることができる。脂肪族類の多価ア
ミンを使用することも可能である。この中でも、多価ア
ミンの第四アンミニウム塩類、例えば３，３′，４，４
′−テトラアミノビフェニル・四塩酸塩等を用いるのが
、中間体的な溶液の状態から三次元網目構造の高分子ゲ
ルに至るまでの時間が比較的長くとれ、均質で良好な成
形体を得る上で好ましい。これらの芳香族トリカルボン
酸無水物のアシルハライド誘導体、芳香族ジアミン及び
多価アミン成分は、それぞれ単独又は二種以上の混合物
で用いられるため、得られる芳香族ポリアミドアミド酸
及びそれを脱水・閉環反応させた芳香族ポリアミドイミ
ドは共重合体のものを含む。また、特定の成分から成る
芳香族ポリアミドアミド酸と、この芳香族ポリアミドア
ミド酸の構成成分の少なくとも一種類が異なる芳香族ポ
リアミドアミド酸を混合した芳香族ポリアミドアミド酸
の混合物、及び、それを脱水・閉環反応させた芳香族ポ
リアミドイミドの混合物も含まれる。芳香族トリカルボ
ン酸無水物のアシルハライド誘導体、芳香族ジアミン及
び多価アミンを主成分とした芳香族ポリアミドアミド酸
の重合において用いられる有機溶媒は、重合反応に対し
て不活性であると同時に、使用するモノマー類及び反応
により生成されたオリゴマーを含む高分子量物を溶解又
は膨潤させる能力のあるもので、代表的なものとして、
Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセ
トアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ，Ｎ−ジ
エチルアセトアミド、ジメチルスルホキシド、Ｎ−メチ
ル−２−ピロリドン、Ｎ，Ｎ−ジメチルメトキシアセト
アミド、ヘキサメチルホスホアミド、ピリジン、ジメチ
ルスルホン、テトラメチレンスルホン、スルホラン、フ
ェノール、キシレノール等のフェノール類や、ベンゼン
、トルエン、キシレン、ベンゾニトリル、ジオキサン、
シクロヘキサン、クロロホルム、１，２ジクロロエタン
等のハロゲン系溶媒等が挙げられる。
これらの溶媒は、単独又は二種以上混合して使用される
。芳香族トリカルボン酸無水物のアシルハライド誘導体
は、芳香族ジアミン及び多価アミンを主成分とした芳香
族ポリアミドアミド酸の重合は、有機溶媒中、−２０〜
８０℃の温度条件下、特に好ましくは０〜３０℃の温度
範囲で反応させる。反応時間は５時間以内、好ましくは
２時間以内である。反応温度が−２０℃より低い場合は
、取扱性や反応方法の難しさに加え、温度が低過ぎるた
め反応自身が十分に進まない場合があり、好ましくない
。反応温度が８０℃を超える場合は、ゲル化に至るまで
の反応が早すぎて、不均質な三次元網目構造の高分子ゲ
ルを与える場合がある。従って、反応温度は、−２０〜
８０℃の温度条件下、特に好ましくは０〜３０℃の温度
範囲で反応させる。この際、重合反応を促進させるため
、触媒としてトリメチルアミン、トリエチルアミンのよ
うな脂肪族第三アミン類、ピリジン、キノリンのような
有機塩基、エチレンオキシド、プロピレンオキシドのよ
うな有機オキシド化合物を、芳香族トリカルボン酸無水
物アシルハライド誘導体の酸クロリド基１当量に対して
０．９〜２モル添加することも可能である。[0008] Polyvalent amine [C] refers to a compound having three or more amine groups and/or ammonium bases in one molecular structure. Representative polyvalent amines include 3,
3',4,4',-tetraaminodiphenyl ether,
3,3',4,4'-tetraaminodiphenylmethane,
3,3',4,4'-tetraaminobenzophenone, 3
,3',4,4'-tetraaminodiphenylsulfone,
3,3',4,4'-tetraaminobiphenyl, 1,2
, 4,5-tetraminobenzene, 3,3',4-triaminodiphenyl ether, 3,3',4-triaminodiphenylmethane, 3,3',4-triaminobenzophenone, 3,3',4-triaminobenzophenone Aminodiphenylsulfone, 3,3',4-triaminobiphenyl, 1,2,4-
Triaminobenzene and compounds obtained by converting the functional groups of these compounds into the form of quaternary ammonium salts, such as 3,3'
, 4,4'-tetraaminobiphenyl tetrahydrochloride and the like. In addition to hydrochloride, quaternary ammonium salts include
It can also be used in the form of P-toluenesulfonate, picrate, etc. Some of these compounds include those in which not all of the functional groups of the polyvalent amine are in the form of quaternary ammonium salts. Further, some of the above substances exist as hydrates, and these polyvalent amines can be used alone or in a mixture of two or more. It is also possible to use polyvalent amines of the aliphatic class. Among these, quaternary amminium salts of polyvalent amines, such as 3,3',4,4
Using ′-tetraaminobiphenyl tetrahydrochloride, etc. takes a relatively long time to transform from an intermediate solution state to a polymer gel with a three-dimensional network structure, resulting in a homogeneous and good molded product. preferred above. These acyl halide derivatives of aromatic tricarboxylic acid anhydrides, aromatic diamines, and polyvalent amine components can be used alone or in a mixture of two or more, so the resulting aromatic polyamide amic acid and its dehydration/ring closure reaction can be The aromatic polyamideimides include copolymers. Further, a mixture of an aromatic polyamide amic acid consisting of a specific component and an aromatic polyamide amic acid in which at least one of the constituent components of the aromatic polyamide amic acid is different, and a mixture thereof, which is dehydrated. - Also includes mixtures of aromatic polyamideimides subjected to ring-closing reaction. The organic solvent used in the polymerization of aromatic polyamide amic acid mainly composed of acyl halide derivatives of aromatic tricarboxylic acid anhydrides, aromatic diamines, and polyvalent amines is inert to the polymerization reaction and at the same time easy to use. It has the ability to dissolve or swell high molecular weight substances including monomers and oligomers produced by reaction, and representative examples include:
N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylmethoxyacetamide, hexamethylphosphor Phenols such as amide, pyridine, dimethylsulfone, tetramethylenesulfone, sulfolane, phenol, xylenol, benzene, toluene, xylene, benzonitrile, dioxane,
Examples include halogen solvents such as cyclohexane, chloroform, and 1,2 dichloroethane. These solvents may be used alone or in combination. Acyl halide derivatives of aromatic tricarboxylic acid anhydrides can be used for polymerization of aromatic polyamide amidic acids containing aromatic diamines and polyvalent amines as main components in an organic solvent of -20 to
The reaction is carried out at a temperature of 80°C, particularly preferably in a temperature range of 0 to 30°C. The reaction time is within 5 hours, preferably within 2 hours. If the reaction temperature is lower than -20°C, it is not preferable because in addition to the difficulty in handling and the reaction method, the reaction itself may not proceed sufficiently because the temperature is too low. If the reaction temperature exceeds 80° C., the reaction leading to gelation may occur too quickly, resulting in a polymer gel with an inhomogeneous three-dimensional network structure. Therefore, the reaction temperature is -20~
The reaction is carried out at a temperature of 80°C, particularly preferably in a temperature range of 0 to 30°C. At this time, in order to accelerate the polymerization reaction, aliphatic tertiary amines such as trimethylamine and triethylamine, organic bases such as pyridine and quinoline, and organic oxide compounds such as ethylene oxide and propylene oxide are used as catalysts, and aromatic tricarboxylic acids are used as catalysts. It is also possible to add 0.9 to 2 moles per equivalent of acid chloride group of the anhydride acyl halide derivative.
【０００９】一般に、芳香族トリカルボン酸無水物のア
シルハライド誘導体と芳香族ジアミンから芳香族ポリア
ミドアミド酸を合成する場合、分子量を上げるために、
両成分を可能な限り等モルで反応させることが好ましい
。本発明でも、芳香族ポリアミドアミド酸の高分子ゲル
の架橋点間分子量と架橋度を最適化するため、芳香族ト
リカルボン酸無水物のアシルハライド誘導体［Ａ］／芳
香族ジアミン［Ｂ］／多価アミン［Ｃ］のモル比を、１
００／（５０〜１００）／（１〜２５）の範囲内にとど
め、且つ、［Ａ］成分の反応基の当量と［Ｂ］及び［Ｃ
］成分の反応基の当量の比［（［Ａ］）成分の反応基の
当量）／（［Ｂ］成分の反応基の当量＋［Ｃ］成分の反
応基の当量）］を０．９０〜１．１０の範囲内（±１０
％以内）に合わせることが、自己支持性のある芳香族ポ
リアミドアミド酸の高分子ゲルを得る上で好ましい。こ
の範囲を外れた組成でモノマーを配合し反応させた場合
、芳香族ポリアミドアミド酸の重合度が上がらず、結果
的に、得られる芳香族ポリアミドアミド酸の高分子ゲル
の性質、例えばゲルの引張り強さや弾性率等の機械的性
質等も低いものとなる。反応させる［Ａ］／［Ｃ］のモ
ル比は、１００／（１〜２５）であることが好ましく、
特に好ましくは、１００／（２〜１５）の範囲であるが
、用いるモノマーの種類により、その好適な組成範囲が
若干ずれる場合もある。多価アミン［Ｃ］は、芳香族ポ
リアミドアミド酸の高分子ゲルの架橋点として働き、そ
の配合比により芳香族ポリアミドアミド酸の高分子ゲル
中に存在する網目濃度（架橋密度）を変化させる。多価
アミン［Ｃ］の配合モル数が、［Ａ］成分１００モルに
対し１モルより小さいと溶液中での芳香族ポリアミドア
ミド酸成分の架橋点が少なくなり、三次元網目構造が不
完全になり、自己支持性のある高分子ゲルとなりにくく
、性質の改善効果が小さい。［Ｃ］成分の配合モル数が
２５モルより大きいと、三次元網目構造の架橋点の増加
と架橋点間分子量の低下を招き、芳香族ポリアミドアミ
ド酸の高分子ゲルの体積膨潤度を低下させ、脆性的な高
分子ゲルとなる傾向が出てくる。従って、［Ｃ］成分の
配合モル数は、［Ａ］成分１００モルに対し１〜２５モ
ルの範囲内がよい。Generally, when synthesizing an aromatic polyamide amic acid from an acyl halide derivative of an aromatic tricarboxylic acid anhydride and an aromatic diamine, in order to increase the molecular weight,
It is preferable to react both components in equimolar amounts as much as possible. In the present invention, in order to optimize the molecular weight between crosslinking points and degree of crosslinking of a polymer gel of aromatic polyamide amic acid, acyl halide derivative [A] of aromatic tricarboxylic acid anhydride/aromatic diamine [B]/polyvalent The molar ratio of amine [C] is 1
00/(50-100)/(1-25), and the equivalent weight of the reactive group of component [A] and [B] and [C
] Ratio of equivalents of reactive groups of components [(equivalents of reactive groups of component [A])/(equivalents of reactive groups of component [B] + equivalents of reactive groups of component [C])] from 0.90 to Within the range of 1.10 (±10
% or less) is preferable in order to obtain a self-supporting aromatic polyamide amic acid polymer gel. If monomers are blended and reacted with a composition outside of this range, the degree of polymerization of the aromatic polyamide amic acid will not increase, and as a result, the properties of the resulting polymer gel of the aromatic polyamide amic acid, such as the tensile strength of the gel. Mechanical properties such as strength and elastic modulus are also low. The molar ratio of [A]/[C] to be reacted is preferably 100/(1 to 25),
Particularly preferably, the range is 100/(2 to 15), but the preferred composition range may vary slightly depending on the type of monomer used. The polyvalent amine [C] acts as a crosslinking point in the polymer gel of aromatic polyamide amic acid, and changes the network density (crosslinking density) present in the polymer gel of aromatic polyamide amic acid depending on its blending ratio. If the blended mole number of polyvalent amine [C] is less than 1 mole per 100 moles of component [A], the number of crosslinking points of the aromatic polyamide amic acid component in the solution will decrease, resulting in an incomplete three-dimensional network structure. Therefore, it is difficult to form a self-supporting polymer gel, and the effect of improving properties is small. If the number of moles of component [C] is greater than 25 moles, the number of crosslinking points in the three-dimensional network structure will increase and the molecular weight between crosslinking points will decrease, leading to a decrease in the degree of volumetric swelling of the polymer gel of aromatic polyamide amic acid. , there is a tendency to form a brittle polymer gel. Therefore, the number of moles of component [C] blended is preferably within the range of 1 to 25 moles per 100 moles of component [A].
【００１０】このようにして得られた芳香族ポリアミド
アミド酸溶液は、前述のように、芳香族ポリアミドアミ
ド酸の高分子ゲルに至るまでの中間体的なものであり、
０〜１００℃の間の温度条件で芳香族ポリアミドアミド
酸溶液を静置することにより重合場に残存する未反応の
官能基による架橋反応が有機溶媒中で徐々に進行するこ
とにより、芳香族ポリアミドアミド酸成分の三次元網目
構造が形成されゲル化を起こし、最終的には、有機溶媒
を含んだ芳香族ポリアミドアミド酸の高分子ゲルを与え
るものである。芳香族ポリアミドアミド酸溶液は高分子
ゲルが生成される前に、特定の形状を持った型に流し込
むか、基材上に流延させゲル化に至らしめる等の方法に
より、特定の形状に賦形された芳香族ポリアミドアミド
酸の高分子ゲルが得られる。有機溶媒を含んだ芳香族ポ
リアミドアミド酸の高分子ゲルより、有機溶媒を除去す
ることにより、フィルム等の成形体が得られる。脱溶媒
は、常圧又は真空下で溶媒を蒸発させるか、有機溶媒の
溶媒置換等の方法により行わせることができる。芳香族
ポリアミドアミド酸の高分子ゲルより、有機溶媒を蒸発
させ除去するためには、常圧又は真空下で２０℃以上の
温度で処理することが好ましい。使用した有機溶媒の沸
点より高い温度で急激に脱溶媒を行わせると、急激な溶
媒の蒸発による成形体の発泡等の不都合が起こり好まし
くない場合がある。脱溶媒により、芳香族ポリアミドア
ミド酸中に含まれる溶媒の含有率を５０重量％以下、好
ましくは４０重量％以下に調整した後、基材上より離脱
させ、芳香族ポリアミドアミド酸の成形体が得られる。
溶媒を含んだ芳香族ポリアミドアミド酸の高分子ゲルを
、芳香族ポリアミドアミド酸の貧溶媒を凝固浴とした浴
中に浸漬せしめ、高分子ゲル中に残存する有機溶媒の溶
媒置換を行わせ、続いて、脱溶媒させることにより、芳
香族ポリアミドアミド酸の成形体を得ることもできる。
この場合、凝固浴としては、水、メタノールやエタノー
ル等のアルコール類、アセトン等のようなケトン類、エ
ーテル類、エステル類などの単独又は混合系が挙げられ
る。少量であれば、Ｎ，Ｎ−ジメチルアセトアミド等の
アミド系溶媒、１，２−ジクロロエタンのような塩素系
溶媒等を凝固液の中に含ませてもよいが、芳香族ポリア
ミドアミド酸を溶解又は膨潤させて、その形状を著しく
損ねるような凝固液は使用できない。芳香族ポリアミド
アミド酸の脱水・閉環反応により、芳香族ポリアミドイ
ミドを得る方法としては、一般のポリアミドイミド樹脂
の調製で用いられている方法と同様の方法で行うことが
できる。芳香族ポリアミドイミドを得る場合は、芳香族
ポリアミドアミド酸を５０〜４００℃の温度で少なくと
も１０秒以上処理する。この際一旦５０〜４００℃で処
理して後、更に処理温度を高め、１５０〜４００℃の多
段の分けて処理することもできる。フィルムの場合は、
一対の両端を固定枠、チャック又はピンガイド等で固定
させて処理すると、寸法安定性や機械的特性に優れたフ
ィルム等の成形物が得られやすい。化学的処理による芳
香族ポリアミドアミド酸の脱水・閉環反応においては、
アミン類を触媒として、酸無水物を脱水剤として用いる
のが効果的である。酸無水物の例としては、無水酢酸、
無水プロピオン酸、無水酪酸などの脂肪族酸無水物、無
水安息香酸などの芳香族酸無水物がある。これらは、単
独又は二種以上の混合物として用いることができる。[0010] The aromatic polyamide amic acid solution thus obtained is, as mentioned above, an intermediate in the process of forming a polymer gel of the aromatic polyamide amic acid.
When the aromatic polyamide amic acid solution is allowed to stand at a temperature between 0 and 100°C, the crosslinking reaction by the unreacted functional groups remaining in the polymerization site gradually proceeds in the organic solvent, resulting in aromatic polyamide A three-dimensional network structure of the amic acid component is formed, causing gelation, and finally a polymer gel of aromatic polyamide amic acid containing an organic solvent is obtained. Before a polymer gel is produced, the aromatic polyamide amic acid solution is shaped into a specific shape by pouring it into a mold with a specific shape or by casting it onto a base material to form a gel. A polymer gel of shaped aromatic polyamide amic acid is obtained. By removing the organic solvent from a polymer gel of aromatic polyamide amic acid containing an organic solvent, a molded article such as a film can be obtained. Solvent removal can be carried out by evaporating the solvent under normal pressure or vacuum, or by replacing the organic solvent with a solvent. In order to evaporate and remove the organic solvent from the aromatic polyamide amic acid polymer gel, it is preferable to perform the treatment at a temperature of 20° C. or higher under normal pressure or vacuum. If the solvent is removed rapidly at a temperature higher than the boiling point of the organic solvent used, problems such as foaming of the molded article due to rapid evaporation of the solvent may occur, which may be undesirable. After adjusting the content of the solvent contained in the aromatic polyamide amic acid to 50% by weight or less, preferably 40% by weight or less by removing the solvent, it is separated from the base material to form a molded article of the aromatic polyamide amic acid. can get. A polymer gel of aromatic polyamideamic acid containing a solvent is immersed in a coagulation bath containing a poor solvent of aromatic polyamideamic acid to perform solvent replacement of the organic solvent remaining in the polymer gel, Subsequently, by removing the solvent, a molded article of aromatic polyamide amic acid can also be obtained. In this case, examples of the coagulation bath include water, alcohols such as methanol and ethanol, ketones such as acetone, ethers, esters, etc. alone or in combination. If it is a small amount, an amide solvent such as N,N-dimethylacetamide, a chlorine solvent such as 1,2-dichloroethane, etc. may be included in the coagulation liquid, but if the aromatic polyamide amic acid is dissolved or It is not possible to use a coagulating liquid that causes swelling and significantly impairs the shape. Aromatic polyamide-imide can be obtained by the dehydration/ring-closing reaction of aromatic polyamide-amic acid in a manner similar to that used in the preparation of general polyamide-imide resins. When obtaining aromatic polyamide-imide, aromatic polyamide-amic acid is treated at a temperature of 50 to 400°C for at least 10 seconds. At this time, after the treatment is performed once at 50 to 400°C, the treatment temperature may be further increased to perform the treatment in multiple stages at 150 to 400°C. For film,
By fixing both ends of the pair with a fixed frame, chuck, pin guide, etc., a molded product such as a film with excellent dimensional stability and mechanical properties can easily be obtained. In the dehydration and ring-closing reaction of aromatic polyamide amic acid by chemical treatment,
It is effective to use amines as a catalyst and acid anhydrides as a dehydrating agent. Examples of acid anhydrides include acetic anhydride,
These include aliphatic acid anhydrides such as propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as benzoic anhydride. These can be used alone or as a mixture of two or more.
【００１１】化学的脱水反応において添加する酸無水物
の量は、芳香族ポリアミドアミド酸に存在するカルボキ
シル基１当量に対して１〜５当量、好ましくは１〜３当
量である。また、アミド酸基の部分的な脱水・閉環反応
によるアミドイミド化でもよい場合は、芳香族ポリアミ
ドアミド酸に存在するカルボキシル基１当量に対して酸
無水物の添加量を１当量以下にしてもよい。触媒として
のアミン類の例は、トリメチルアミン、トリエチルアミ
ン、トリエチレンジアミン、トリブチルアミン、ジメチ
ルアニリン、ピリジン、α−ピコリン、β−ピコリン、
γ−ピコリン、イソキノリン、ルチジン等の第３級アミ
ンの中から選ばれる少なくとも一種のアミン類である。
また、酢酸コバルト、酢酸ニッケル等のカルボン酸金属
塩も使用できる。触媒の量は、芳香族ポリアミドアミド
酸に存在するカルボキシル基１当量に対して０．０１〜
１．５当量、好ましくは０．２〜１当量である。予め芳
香族ポリアミドアミド酸のゲルを形成させる以前に、上
記の脱水剤などを含ませておき、成形体を形成させた後
に化学的処理による脱水・閉環反応を行わせてもよい。
以上のようにして、芳香族ポリアミドアミド酸の高分子
ゲルよりフイルム等の成形体、更には、芳香族ポリアミ
ドアミド酸成分の脱水・閉環反応により芳香族ポリアミ
ドイミドの成形体を調製することができる。芳香族ホリ
アミドアミド酸に、第三成分を複合させる場合は、第三
成分を有機溶媒に溶解又は分散させた状態で、本発明の
特定モノマーより構成された芳香族ポリアミドアミド酸
溶液に加えられ、複合化が行われる。更には、この芳香
族ポリアミドアミド酸／第三成分の複合体を脱水・閉環
反応させた芳香族ポリアミドイミド／第三成分の複合体
を調製することもできる。The amount of acid anhydride added in the chemical dehydration reaction is 1 to 5 equivalents, preferably 1 to 3 equivalents, per equivalent of carboxyl group present in the aromatic polyamide amic acid. In addition, if amide imidization by partial dehydration/ring closure reaction of the amic acid group is acceptable, the amount of acid anhydride added may be 1 equivalent or less per 1 equivalent of carboxyl group present in the aromatic polyamide amic acid. . Examples of amines as catalysts include trimethylamine, triethylamine, triethylenediamine, tributylamine, dimethylaniline, pyridine, α-picoline, β-picoline,
At least one amine selected from tertiary amines such as γ-picoline, isoquinoline, and lutidine. Further, carboxylic acid metal salts such as cobalt acetate and nickel acetate can also be used. The amount of catalyst is 0.01 to 1 equivalent of carboxyl group present in the aromatic polyamide amic acid.
The amount is 1.5 equivalents, preferably 0.2 to 1 equivalent. Before forming a gel of aromatic polyamide amic acid, the above-mentioned dehydrating agent may be impregnated in advance, and after forming a molded product, dehydration and ring-closing reactions may be performed by chemical treatment. As described above, molded bodies such as films can be prepared from the polymer gel of aromatic polyamide amic acid, and further, molded bodies of aromatic polyamide imide can be prepared by dehydration and ring-closing reaction of the aromatic polyamide amic acid component. . When a third component is combined with aromatic polyamide amic acid, the third component is dissolved or dispersed in an organic solvent and added to the aromatic polyamide amic acid solution composed of the specific monomer of the present invention. , decoding is performed. Furthermore, it is also possible to prepare an aromatic polyamideimide/third component composite by subjecting this aromatic polyamide amic acid/third component composite to a dehydration/ring-closing reaction.
【００１２】第三成分として、例えば、低分子有機化合
物、無機物質、金属化合物、高分子化合物等を含ませる
場合には、予め有機溶媒中に第三成分を含ませた溶液中
で芳香族トリカルボン酸無水物のアシルハライド誘導体
、芳香族ドアミン及び多価アミン成分の重合反応を行わ
せるか、又は、重合反応により得られた有機溶媒に均一
に溶解した芳香族ポリアミドアミド酸溶液に、第三成分
を添加する等の方法により、第三成分との複合化を行わ
せる。このような芳香族ポリアミドアミド酸の高分子ゲ
ル及び高分子ゲルを経由して作られた成形体に関する調
製方法は、これまで例がなく新規なものであり、得られ
た芳香族ポリアミドアミド酸の高分子ゲル、又は、この
高分子ゲルから溶媒を除去させて得られた成形体、更に
は、脱水・閉環反応によって得られた芳香族ポリアミド
イミドは、多価アミンを架橋点として三次元網目構造を
形成している特異な高分子構造体である。本発明で得ら
れた有機溶媒を含んだ芳香族ポリアミドアミド酸の高分
子ゲルにおいて、芳香族ポリアミドアミド酸は多価アミ
ンを架橋点として、主に共有結合、イオン結合及び水素
結合的な三次元網目構造を形成するものであり、多量の
有機溶媒を含んでも自己支持性の高分子ゲルを与えるも
のである。このような調製方法により得られた芳香族ポ
リアミドアミド酸の高分子ゲルは、有機溶媒中で２〜５
０倍の体積膨潤度を示す新しい構造の高分子ゲルであり
、溶媒の出入りにより可逆的に収縮・膨潤を繰り返す構
造体である。芳香族ポリアミドアミド酸の高分子ゲルの
体積膨潤度は、芳香族ポリアミドアミド酸を形成するモ
ノマー成分の種類や配合比による架橋密度の変化、高分
子ゲル中に含まれる有機溶媒の種類により２〜５０倍の
範囲内で変化し、架橋密度をコントロールすることによ
り、一定の体積膨潤度を持つ芳香族ポリアミドアミド酸
の高分子ゲルを調製することも可能である。本発明で得
られた有機溶媒を含んだ芳香族ポリアミドアミド酸の高
分子ゲルにおいて、溶媒の出入りによる収縮・膨潤する
現象は可逆的であるため、この力学エネルギーを利用し
て、化学センサー、スイッチ、アクチュエーターに有用
である。また、高分子ゲルの三次元網目構造の架橋密度
を変化させたものは、物質分離能が付与され、分離膜、
分離用担体等に用いられる。また、芳香族ポリアミドア
ミド酸の高分子ゲルを経由して、脱溶媒の後に脱水・閉
環反応によって得られた芳香族ポリアミドイミドの成形
体は、耐熱性と成形性を兼備した有用なものであり、各
種成形材料、特殊フィルム、特殊繊維の原料として使用
できる。調製方法によっては多孔性の材料を成形品とし
て作製することもでき、物質分離作用のある機能性高分
子材料となる。更に、芳香族ポリアミドイミドを調製後
、高温処理により成形体の性質を改良し、通電性等のよ
うな電気的性質等を付与させ、導電性フィルム、電極材
等にも応用できる。When containing a low-molecular organic compound, an inorganic substance, a metal compound, a polymer compound, etc. as the third component, aromatic tricarboxylic acid is added in advance in a solution containing the third component in an organic solvent. Either the acyl halide derivative of the acid anhydride, the aromatic door amine, and the polyvalent amine component are subjected to a polymerization reaction, or the third component is added to an aromatic polyamide amic acid solution uniformly dissolved in an organic solvent obtained by the polymerization reaction. Compositeization with a third component is performed by a method such as adding . The preparation method for such a polymer gel of aromatic polyamide amic acid and a molded article made via the polymer gel is unprecedented and novel. Polymer gels, molded bodies obtained by removing the solvent from these polymer gels, and aromatic polyamideimides obtained by dehydration and ring closure reactions have a three-dimensional network structure using polyvalent amines as crosslinking points. It is a unique polymer structure that forms a In the polymer gel of aromatic polyamideamic acid containing an organic solvent obtained in the present invention, the aromatic polyamideamic acid uses polyvalent amines as crosslinking points, and mainly forms three-dimensional bonds such as covalent bonds, ionic bonds, and hydrogen bonds. It forms a network structure and provides a self-supporting polymer gel even if it contains a large amount of organic solvent. A polymer gel of aromatic polyamide amic acid obtained by such a preparation method can be prepared in an organic solvent for 2 to 5 days.
It is a polymer gel with a new structure that exhibits a volumetric swelling degree of 0 times, and it is a structure that repeatedly contracts and swells reversibly as a solvent enters and exits. The degree of volumetric swelling of the polymer gel of aromatic polyamide amic acid varies from 2 to 2 depending on the type and blending ratio of monomer components forming the aromatic polyamide amic acid, changes in crosslinking density depending on the blending ratio, and the type of organic solvent contained in the polymer gel. By controlling the crosslinking density, it is also possible to prepare a polymer gel of aromatic polyamide amic acid having a constant volume swelling degree, which varies within a 50-fold range. In the polymer gel of aromatic polyamidoamic acid containing an organic solvent obtained in the present invention, the contraction and swelling phenomenon due to the inflow and outflow of the solvent is reversible, so this mechanical energy can be used to create chemical sensors, switches, etc. , useful for actuators. In addition, polymer gels with different crosslinking densities in their three-dimensional network structure have substance separation ability, and can be used as separation membranes,
Used as separation carriers, etc. In addition, a molded article of aromatic polyamide-imide obtained by desolvation, dehydration, and ring-closing reaction via a polymer gel of aromatic polyamide-amic acid is useful because it has both heat resistance and moldability. It can be used as a raw material for various molding materials, special films, and special fibers. Depending on the preparation method, the porous material can be made into a molded article, resulting in a functional polymeric material that has a substance separation effect. Furthermore, after preparing the aromatic polyamide-imide, the properties of the molded product are improved by high-temperature treatment to impart electrical properties such as electrical conductivity, and the product can be applied to conductive films, electrode materials, etc.
【００１３】[0013]
【実施例１】３００ｍｌの四つ口セパラブルフラスコ中
に、３．３３１ｇ（０．０１６８モル）の精製した４，
４′−ジアミノジフェニルメタン（略称：４，４′−Ｄ
ＤＭ）と０．６３３６ｇ（０．００１６モル）の３，３
′，４，４′−テトラアミノビフェニル・四塩酸塩・二
水和物（略称：ＴＡＢＴ）を採取し、５０ｇの蒸留され
たＮ−メチル−２−ピロリドン（略称：ＮＭＰ）を加え
、攪拌し溶解させて溶液を得た。窒素雰囲気の下、外部
水槽の温度を０℃にコントロールし、上記溶液を攪拌し
ながら４．２１２ｇ（０．０２モル）の精製した４−（
クロロホルミル）無水フタル酸（略称：ＣＰＡ）を固形
のまま、溶液の温度が上らないように注意しながら徐々
に添加し、全て加え終った後、攪拌を続け均一な芳香族
ポリアミドアミド酸溶液を調製した。この芳香族ポリア
ミドアミド酸溶液をガラス板上に流延した。溶液の塗布
量は、スペーサーによりコントロールし、約０．４ｍｍ
の厚さになるようにした。しばらく静置すると、流延さ
れた芳香族ポリアミドアミド酸溶液がゲル化を起こし、
芳香族ポリアミドアミド酸の高分子ゲル（高分子ゲルフ
ィルム）が得られた。この芳香族ポリアミドアミド酸高
分子ゲルは、自重による形状変化を起こさず、自己支持
性のものであった。この芳香族ポリアミドアミド酸の高
分子ゲルを５０℃で真空乾燥させ、高分子ゲルの中の溶
媒を飛散させた後、フィルム状の形でガラス板より離脱
させた。このフィルムを、ＮＭＰ溶媒中に浸漬させたと
ころ、フィルムが膨潤し体積膨潤度は９．５倍を示した
。更に、５０℃で真空乾燥させ、高分子ゲルの中の溶媒
を飛散させると、元のフィルム状の形状に戻り、溶媒の
出入りにより収縮・膨潤を繰り返すことが確認された。
このフィルムを１５０℃で２時間、２００℃で２時間、
３００℃で１時間処理し、フィルムの赤外線吸収スペク
トルを測定した。１７８０ｃｍ−１、１７２０ｃｍ−１
にイミド基の特性吸収帯が観測され、このフィルムが芳
香族ポリアミドイミドであることが確認された。このフ
ィルムについて熱機械分析（ＴＭＡ）を行ったところ、
２８０℃にポリマーの二次転移に対応する熱膨張曲線の
変化が観測され、４５０℃以上で分解によるフィルムの
収縮が認められた。フィルムに関し、引張り強さは１５
．０ｋｇｆ／ｍｍ２、弾性率は３５０ｋｇｆ／ｍｍ２で
あった。[Example 1] In a 300 ml four-necked separable flask, 3.331 g (0.0168 mol) of purified 4,
4'-diaminodiphenylmethane (abbreviation: 4,4'-D
DM) and 0.6336 g (0.0016 mol) of 3,3
Collect ',4,4'-tetraaminobiphenyl tetrahydrochloride dihydrate (abbreviation: TABT), add 50 g of distilled N-methyl-2-pyrrolidone (abbreviation: NMP), and stir. A solution was obtained by dissolving. 4.212 g (0.02 mol) of purified 4-(
Add chloroformyl) phthalic anhydride (abbreviation: CPA) as a solid while being careful not to raise the temperature of the solution. After all the addition is complete, continue stirring to form a homogeneous aromatic polyamide amidic acid solution. was prepared. This aromatic polyamide amic acid solution was cast onto a glass plate. The amount of solution applied is controlled by a spacer, approximately 0.4 mm.
The thickness was set to . When left standing for a while, the cast aromatic polyamide amic acid solution undergoes gelation.
A polymer gel (polymer gel film) of aromatic polyamide amic acid was obtained. This aromatic polyamide amic acid polymer gel did not change shape due to its own weight and was self-supporting. This polymer gel of aromatic polyamide amic acid was vacuum dried at 50° C. to scatter the solvent in the polymer gel, and then separated from the glass plate in the form of a film. When this film was immersed in an NMP solvent, the film swelled and the degree of volumetric swelling was 9.5 times. Furthermore, it was confirmed that when the polymer gel was dried under vacuum at 50° C. to scatter the solvent in the polymer gel, it returned to its original film-like shape and repeatedly contracted and swelled due to the inflow and outflow of the solvent. This film was heated at 150℃ for 2 hours and at 200℃ for 2 hours.
After processing at 300° C. for 1 hour, the infrared absorption spectrum of the film was measured. 1780cm-1, 1720cm-1
A characteristic absorption band of imide groups was observed, confirming that this film was an aromatic polyamide-imide. When thermomechanical analysis (TMA) was performed on this film,
A change in the thermal expansion curve corresponding to the second-order transition of the polymer was observed at 280°C, and shrinkage of the film due to decomposition was observed at 450°C or higher. Regarding the film, the tensile strength is 15
．． The elastic modulus was 350 kgf/mm2.
【００１４】[0014]
【比較例１】（［Ａ］成分不使用）３００ｍｌの四つ口
セパラブルフラスコ中に、３．９６６ｇ（０．０２モル
）の精製した４，４′−ジアミノジフェニルメタンを採
取し、５０ｇの蒸留されたＮ−メチル−２−ピロリドン
（略称：ＮＭＰ）を加え、攪拌し溶解させて溶液を得た
。窒素雰囲気の下、外部水槽の温度を０℃にコントロー
ルし、上記溶液を攪拌しながら４．２１２ｇ（０．０２
モル）の精製した４−（クロロホルミル）無水フタル酸
を固形のまま、溶液の温度が上らないように注意しなが
ら徐々に添加し、全て加え終った後、攪拌を続け均一な
芳香族ポリアミドアミド酸溶液を調製した。実施例１と
同様に、芳香族ポリアミドアミド酸溶液をガラス板上に
流延させ静置させたが、室温で５時間放置しても溶液は
高分子ゲルを形成せず、この溶液は自重により流動した
。また、この芳香族ポリアミドアミド酸溶液から、実施
例１と同様に溶媒の除去と熱処理を行って芳香族ポリア
ミドイミドのフィルムを調製した。得られたフィルムは
、実施例１と同様の熱膨張挙動を示したが、フィルムに
関し、引張り強さは７．０ｋｇｆ／ｍｍ２、弾性率は３
７０ｋｇｆ／ｍｍ２であり、実施例１に比し脆性的なフ
ィルムであった。[Comparative Example 1] (Component [A] not used) 3.966 g (0.02 mol) of purified 4,4'-diaminodiphenylmethane was collected in a 300 ml four-neck separable flask, and 50 g of distilled N-methyl-2-pyrrolidone (abbreviation: NMP) was added and stirred to dissolve it to obtain a solution. Under a nitrogen atmosphere, the temperature of the external water tank was controlled at 0°C, and while stirring the above solution, 4.212g (0.02g
mol) of purified 4-(chloroformyl)phthalic anhydride is gradually added as a solid while being careful not to raise the temperature of the solution. After all the addition is complete, stirring is continued until a homogeneous aromatic polyamide is formed. An amic acid solution was prepared. As in Example 1, an aromatic polyamide amic acid solution was cast onto a glass plate and left to stand, but even after being left at room temperature for 5 hours, the solution did not form a polymer gel, and due to its own weight, the solution It flowed. Further, from this aromatic polyamide-amic acid solution, the solvent was removed and heat treated in the same manner as in Example 1 to prepare an aromatic polyamide-imide film. The obtained film showed the same thermal expansion behavior as Example 1, but the film had a tensile strength of 7.0 kgf/mm2 and an elastic modulus of 3.
The film was 70 kgf/mm2 and was more brittle than that of Example 1.
【００１５】[0015]
【実施例２】３００ｍｌの四つ口セパラブルフラスコ中
に、０．９７３ｇ（０．００９モル）の精製したパラフ
ェニレンジアミンと１．８８２ｇ（０．００９４ル）の
４，４′−ジアミノジフェニルエーテル（略称：４，４
′−ＤＰＥ）及び０．３１６８ｇ（０．０００８モル）
の３，３′，４，４′−テトラアミノビフェニル・四塩
酸塩・二水和物（略称：ＴＡＢＴ）を採取し、５０ｇの
蒸留されたＮ−メチル−２−ピロリドン（略称：ＮＭＰ
）を加え、攪拌し溶解させて溶液を得た。窒素雰囲気の
下、外部水槽の温度を−５℃にコントロールし、上記溶
液を攪拌しながら４．２１２ｇ（０．０２モル）の精製
した４−（クロロホルミル）無水フタル酸（略称：ＣＰ
Ａ）を固形のまま、溶液の温度が上らないように注意し
ながら徐々に添加し、全て加え終った後、攪拌を続け均
一な芳香族ポリアミドアミド酸溶液を調製した。実施例
１と同様に、この芳香族ポリアミドアミド酸溶液をガラ
ス板上に流延し静置したところ、溶液がゲル化を起こし
、芳香族ポリアミドアミド酸の高分子ゲル（高分子ゲル
フィルム）が得られた。このものは、自重による形状変
化を起こさず、自己支持性のものであった。この芳香族
ポリアミドアミド酸高分子ゲルを５０℃で真空乾燥させ
、高分子ゲルの中の溶媒を飛散させた後、フィルム状の
形でガラス板より離脱させた。このフィルムを、Ｎ，Ｎ
−ジメチルアセトアミド（略称：ＤＭＡｃ）溶媒中に浸
漬させたところ、フィルムが膨潤し体積膨潤度は１７．
０倍を示した。更に、このフィルム高分子ゲルをベンゼ
ンに浸漬させると体積膨潤度は１．５倍に減少し、続い
て、ＤＭＡｃ溶媒に再度浸漬させたところ、フィルムが
膨潤し体積膨潤度は１７．０倍に戻った。このように、
上記フィルムは溶媒の出入りにより収縮・膨潤を繰り返
すことが確認された。実施例１と同様に熱処理を行い、
芳香族ポリアミドイミドフィルムの特性を評価した。フ
ィルムのＴＭＡ測定より、３２０℃に二次転移に対応す
る熱膨張曲線の変化が観測された。フィルムに関し、引
張り強さは１３．５ｋｇｆ／ｍｍ２、弾性率は３８０ｋ
ｇｆ／ｍｍ２であった。Example 2 In a 300 ml four-necked separable flask, 0.973 g (0.009 mol) of purified para-phenylene diamine and 1.882 g (0.0094 mol) of 4,4'-diaminodiphenyl ether ( Abbreviation: 4,4
'-DPE) and 0.3168 g (0.0008 mol)
3,3',4,4'-tetraaminobiphenyl tetrahydrochloride dihydrate (abbreviation: TABT) was collected, and 50 g of distilled N-methyl-2-pyrrolidone (abbreviation: NMP) was collected.
) was added, stirred and dissolved to obtain a solution. Under a nitrogen atmosphere, the temperature of the external water bath was controlled at -5°C, and while stirring the above solution, 4.212 g (0.02 mol) of purified 4-(chloroformyl)phthalic anhydride (abbreviation: CP) was added.
A) was gradually added in a solid state while being careful not to raise the temperature of the solution, and after the addition was complete, stirring was continued to prepare a homogeneous aromatic polyamide amic acid solution. As in Example 1, when this aromatic polyamide amic acid solution was cast onto a glass plate and left to stand, the solution gelled and a polymer gel (polymer gel film) of aromatic polyamide amic acid formed. Obtained. This product did not change shape due to its own weight and was self-supporting. This aromatic polyamide amic acid polymer gel was vacuum dried at 50° C. to scatter the solvent in the polymer gel, and then separated from the glass plate in the form of a film. This film is
- When immersed in dimethylacetamide (abbreviation: DMAc) solvent, the film swelled and the degree of volumetric swelling was 17.
It showed 0 times. Furthermore, when this film polymer gel was immersed in benzene, the degree of volume swelling decreased to 1.5 times, and when it was then immersed again in DMAc solvent, the film swelled and the degree of volume swelling decreased to 17.0 times. I'm back. in this way,
It was confirmed that the above film repeatedly shrinks and swells due to the ingress and egress of the solvent. Heat treatment was performed in the same manner as in Example 1,
The properties of aromatic polyamideimide film were evaluated. Through TMA measurement of the film, a change in the thermal expansion curve corresponding to a second-order transition was observed at 320°C. Regarding the film, the tensile strength is 13.5kgf/mm2 and the elastic modulus is 380k.
gf/mm2.
【００１６】[0016]
【実施例３】３００ｍｌの四つ口セパラブルフラスコ中
に、２．４６２ｇ（０．０１２３モル）の精製した４，
４′−ジアミノジフェニルエーテルと０．３９６ｇ（０
．００１モル）の３，３′，４，４′−テトラアミノビ
フェニル・四塩酸塩・二水和物を採取し、４０ｇの蒸留
されたＮ，Ｎ−ジメチルアセトアミドを加え、攪拌し溶
解させて溶液を得た。窒素雰囲気の下、外部水槽の温度
を０℃にコントロールし、上記溶液を攪拌しながら２．
９４８ｇ（０．０１４モル）の精製した４−（クロロホ
ルミル）無水フタル酸を固形のまま、溶液の温度が上ら
ないように注意しながら徐々に添加した。別の３００ｍ
ｌの四つ口セパラブルフラスコ中に、今度は１．４６２
ｇ（０．００５モル）の精製した１，４−ビス（４−ア
ミノフェノキシ）ベンゼン（略称：ＴＰＥ−Ｑ）と０．
１１８８ｇ（０．０００３モル）の３，３′，４，４′
−テトラアミノビフェニル・四塩酸塩・二水和物を採取
し、３０ｇの蒸留されたＮ−メチル−２−ピロリドンを
加え、攪拌し溶解させて溶液を得た。同様に、窒素雰囲
気の下、外部水槽の温度を０℃にコントロールし、上記
溶液を攪拌しながら１．２６４ｇ（０．００６モル）の
精製した４−（クロロホルミル）無水フタル酸を固形の
まま、溶液の温度が上らないように注意しながら徐々に
添加した。この二種の反応液を、温度を０℃にコントロ
ールしたまま、混合、攪拌し、均一な芳香族ポリアミド
アミド酸溶液を調製した。実施例１と同様に、この芳香
族ポリアミドアミド酸の溶液をガラス板上に流延し静置
したところ、溶液がゲル化を起こし、複合された芳香族
ポリアミドアミド酸の高分子ゲル（高分子ゲルフィルム
）が得られた。このものは、自重による形状変化を起こ
さず、自己支持性のものであった。この芳香族ポリアミ
ドアミド酸を３０℃で真空乾燥させ、高分子ゲルの中の
溶媒を飛散させた後、フィルム状の形でガラス板より離
脱させた。このフィルムをジメチルホルムアミド（ＤＭ
Ｆ）溶媒中に浸漬させたところ、フィルムが膨潤し体積
膨潤度は１５．０倍を示した。実施例１と同様に熱処理
を行い、得られた芳香族ポリアミドイミドフィルムの熱
的及び機械的性質を評価した。ＴＭＡ測定では、２６０
℃に二次転移に対応する熱膨張曲線の変化が観測された
。フィルムに関し、引張り強さは１２．５ｋｇｆ／ｍｍ
２、弾性率は２９０ｋｇｋｇｆ／ｍｍ２であった。[Example 3] In a 300 ml four-neck separable flask, 2.462 g (0.0123 mol) of purified 4,
4'-diaminodiphenyl ether and 0.396 g (0
．． 001 mol) of 3,3',4,4'-tetraaminobiphenyl tetrahydrochloride dihydrate was collected, 40 g of distilled N,N-dimethylacetamide was added, and the solution was dissolved by stirring. I got it. 2. Under a nitrogen atmosphere, the temperature of the external water tank was controlled at 0°C, and the above solution was stirred.
948 g (0.014 mol) of purified 4-(chloroformyl)phthalic anhydride was gradually added in solid form while being careful not to raise the temperature of the solution. another 300m
In a 4-necked separable flask, this time 1.462
g (0.005 mol) of purified 1,4-bis(4-aminophenoxy)benzene (abbreviation: TPE-Q) and
1188g (0.0003 mol) of 3,3',4,4'
-Tetraaminobiphenyl tetrahydrochloride dihydrate was collected, 30 g of distilled N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved to obtain a solution. Similarly, under a nitrogen atmosphere, the temperature of the external water tank was controlled at 0°C, and while stirring the above solution, 1.264 g (0.006 mol) of purified 4-(chloroformyl)phthalic anhydride was added as a solid. was added gradually, taking care not to raise the temperature of the solution. These two reaction solutions were mixed and stirred while controlling the temperature at 0° C. to prepare a homogeneous aromatic polyamide amic acid solution. In the same manner as in Example 1, when this solution of aromatic polyamide amic acid was cast on a glass plate and left to stand, the solution gelled, forming a polymer gel (polymer gel film) was obtained. This product did not change shape due to its own weight and was self-supporting. This aromatic polyamideamic acid was vacuum dried at 30° C. to scatter the solvent in the polymer gel, and then separated from the glass plate in the form of a film. This film was coated with dimethylformamide (DM).
F) When immersed in a solvent, the film swelled and the degree of volumetric swelling was 15.0 times. Heat treatment was performed in the same manner as in Example 1, and the thermal and mechanical properties of the obtained aromatic polyamide-imide film were evaluated. In TMA measurement, 260
A change in the thermal expansion curve corresponding to a second-order transition was observed at °C. Regarding the film, the tensile strength is 12.5 kgf/mm
2. The elastic modulus was 290 kgkgf/mm2.
【００１７】[0017]
【実施例４】３００ｍｌの四つ口セパラブルフラスコ中
に、１．００１ｇ（０．００５モル）の精製した３，４
′−ジアミノジフェニルエーテル（略称：３，４′−Ｄ
ＰＥ）と１．０６２ｇ（０．００５モル）の０−トルイ
ジンを採取し、２０ｇの蒸留されたＮ−メチル−２−ピ
ロリドを加え、攪拌し溶解させて溶液を得た。窒素雰囲
気の下、外部水槽の温度を−５℃にコントロールし、上
記溶液を攪拌しながら２．１０６ｇ（０．０１モル）の
精製した４−（クロロホルミル）無水フタル酸を固形の
まま、溶液の温度が上らないように注意しながら徐々に
添加し、全て加え終わった後、攪拌を続け均一な芳香族
ポリアミドアミド酸溶液を調製した。別の３００ｍｌの
四つ口セパラブルフラスコ中に、１．６８２ｇ（０．０
０８４モル）の精製した４，４′−ジアミノジフェニル
エーテルと０．３１６８ｇ（０．０００８モル）の３，
３′，４，４’−テトラアミノビフェニル・四塩酸塩・
二水和物を採取し、３０ｇの蒸留されたＮ−ジメチルア
セトアミドを加え、攪拌し溶解させて溶液を得た。
窒素雰囲気の下、外部水槽の温度を−５℃にコントロー
ルし、上記溶液を攪拌しながら２．１０６ｇ（０．０１
モル）の精製した４−（クロロホルミル）無水フタル酸
を固形のまま、溶液の温度が上らないように注意しなが
ら徐々に添加した。この二種の反応液を、温度を−５℃
コントロールしたまま、混合、攪拌し、均一な芳香族ポ
リアミドアミド酸溶液を調製した。後は、実施例３と同
様な方法で芳香族ポリアミドアミド酸の高分子ゲル及び
フィルムの調製を行い、特性を調べた。ＴＭＡ測定では
、２７５℃に二次転移に対応する熱膨脹曲線の変化が観
測された。フィルムに関し、引張り強さは１１．５ｋｇ
ｆ／ｍｍ２、弾性率は３２０ｋｇｆ／ｍｍ２であった。[Example 4] In a 300 ml four-necked separable flask, 1.001 g (0.005 mol) of purified 3,4
'-Diaminodiphenyl ether (abbreviation: 3,4'-D
PE) and 1.062 g (0.005 mol) of 0-toluidine were collected, and 20 g of distilled N-methyl-2-pyrrolide was added thereto and dissolved by stirring to obtain a solution. Under a nitrogen atmosphere, the temperature of the external water tank was controlled at -5°C, and while stirring the above solution, 2.106 g (0.01 mol) of purified 4-(chloroformyl)phthalic anhydride was added as a solid to the solution. The mixture was gradually added while being careful not to raise the temperature of the mixture, and after the addition was complete, stirring was continued to prepare a homogeneous aromatic polyamide amic acid solution. In another 300 ml four-neck separable flask, 1.682 g (0.0
084 mol) of purified 4,4'-diaminodiphenyl ether and 0.3168 g (0.0008 mol) of 3,
3',4,4'-tetraaminobiphenyl tetrahydrochloride
The dihydrate was collected and 30 g of distilled N-dimethylacetamide was added and stirred to dissolve it to obtain a solution. Under a nitrogen atmosphere, the temperature of the external water tank was controlled at -5℃, and while stirring the above solution, 2.106g (0.01g
mol) of purified 4-(chloroformyl)phthalic anhydride was gradually added in solid form while being careful not to raise the temperature of the solution. These two reaction solutions were heated to -5°C.
Mixing and stirring were carried out under control to prepare a homogeneous aromatic polyamide amic acid solution. Thereafter, polymer gels and films of aromatic polyamide amic acid were prepared in the same manner as in Example 3, and their properties were investigated. In the TMA measurement, a change in the thermal expansion curve corresponding to a second-order transition was observed at 275°C. Regarding the film, the tensile strength is 11.5 kg
f/mm2, and the elastic modulus was 320 kgf/mm2.
Claims (5)
を有機溶媒中で重合反応させて得た芳香族ポリアミドア
ミド酸の三次元網目構造体。 ［Ａ］下式で表わされる芳香族トリカルボン酸無水物の
アシルハライド誘導体の単独又は二種以上の組み合わせ
【化１】 （式中、Ａは三価の芳香族基、Ｘはハロゲン原子を表わ
す） ［Ｂ］下式で表わされる芳香族ジアミンの単独又は二種
以上の組み合わせ 【化２】 （式中、Ｂは二価の芳香族基を表わす）［Ｃ］ひとつの
分子構造中に三個以上のアミン基及び／又はアンモニウ
ム塩基を有する多価アミンの単独又は二種以上の組み合
わせ1. A three-dimensional network structure of aromatic polyamide amic acid obtained by polymerizing the following components [A], [B], and [C] in an organic solvent. [A] An acyl halide derivative of an aromatic tricarboxylic acid anhydride represented by the following formula or a combination of two or more [Formula 1] (wherein A represents a trivalent aromatic group and X represents a halogen atom) [B] One or more aromatic diamines represented by the following formula [Chemical formula 2] (In the formula, B represents a divalent aromatic group) [C] Three or more aromatic diamines in one molecular structure Single or a combination of two or more polyvalent amines having amine groups and/or ammonium bases
ル比が、１００／（５０〜１００）／（１〜２５）であ
る請求項１記載の芳香族ポリアミドアミド酸の三次元網
目構造体。2. The three-dimensional aromatic polyamide amic acid according to claim 1, wherein the molar ratio of the [A]/[B]/[C] components is 100/(50-100)/(1-25). mesh structure.
としたモノマー類を有機溶媒中で重合反応させて得られ
た芳香族ポリアミドアミド酸溶液を０〜８０℃に保つこ
とで芳香族ポリアミドアミド酸の架橋反応を溶液中で進
め芳香族ポリアミドアミド酸の高分子ゲルとし、次いで
有機溶媒を除去することによる請求項１記載の芳香族ポ
リアミドアミド酸の三次元網目構造体の製造方法。3. An aromatic polyamide amic acid solution obtained by polymerizing monomers mainly composed of components [A], [B], and [C] in an organic solvent is maintained at a temperature of 0 to 80°C. The method for producing a three-dimensional network structure of aromatic polyamide amic acid according to claim 1, which comprises carrying out a crosslinking reaction of the group polyamide amic acid in a solution to form a polymer gel of aromatic polyamide amic acid, and then removing the organic solvent. .
とした請求項１記載の芳香族ポリアミドアミド酸の三次
元網目構造体を、脱水・閉環反応させることにより得ら
れた芳香族ポリアミドイミドの三次元網目構造体。4. An aromatic compound obtained by dehydrating and ring-closing the three-dimensional network structure of the aromatic polyamide amic acid according to claim 1, which contains components [A], [B], and [C] as main components. Three-dimensional network structure of polyamideimide.
とした請求項１記載の芳香族ポリアミドアミド酸の三次
元網目構造体を５０〜４００℃の温度で少なくとも１０
秒以上処理し、脱水・閉環反応させることによる請求項
４記載の芳香族ポリアミドイミドの三次元網目構造体の
製造方法。5. The three-dimensional network structure of the aromatic polyamide amic acid according to claim 1, which contains components [A], [B], and [C] as main components, is heated at a temperature of 50 to 400°C for at least 10
5. The method for producing a three-dimensional network structure of aromatic polyamide-imide according to claim 4, which comprises treating for more than a second to cause a dehydration/ring closure reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41886790A JPH04249533A (en) | 1990-12-28 | 1990-12-28 | Three-dimensional network structure of aromatic polyamideamic acid and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41886790A JPH04249533A (en) | 1990-12-28 | 1990-12-28 | Three-dimensional network structure of aromatic polyamideamic acid and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04249533A true JPH04249533A (en) | 1992-09-04 |
Family
ID=18526623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41886790A Pending JPH04249533A (en) | 1990-12-28 | 1990-12-28 | Three-dimensional network structure of aromatic polyamideamic acid and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04249533A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012530154A (en) * | 2009-06-11 | 2012-11-29 | ケース ウエスタン リザーブ ユニバーシティ | Low density hydrophobic substance and method for producing the same |
-
1990
- 1990-12-28 JP JP41886790A patent/JPH04249533A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012530154A (en) * | 2009-06-11 | 2012-11-29 | ケース ウエスタン リザーブ ユニバーシティ | Low density hydrophobic substance and method for producing the same |
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